Aspirin purity by Titration

Purpose of this Experiment:

• To determine the purity of synthesized aspirin sample by acid-base
titration, and to compare the results with those from pure salicylic
acid, acetylsalicylic acid, and with commercial aspirin tablets.
Aspirin uses
• an analgesic (pain-killer)
• antipyretic (fever-reducer)

It has mild short-term analgesic effect,

long-range benefits, including reducing the probability of users'
suffering heart attacks and colon cancer.
• In the nineteenth century, chemists isolated salicylic acid from willow
twigs and showed that it was the effective ingredient.
• Pure salicylic acid is very damaging to the stomach, and the acetyl
derivative was prepared in order to reduce this undesirable side
effect.
• Acetylsalicylic acid has become the most extensively used
pharmaceutical product in the world
• On standing for prolonged periods of time in a humid atmosphere,
aspirin tablets develop a vinegary smell due to the hydrolysis of
acetylsalicylic acid (ASA) to form salicylic acid (SA).
• A hydrolysis is a reaction with water to break one or more bonds. In
this case, the acetyl group comes off as acetic acid, which causes the
vinegary smell.
• In this exercise, we will determine by acid-base titration the amounts
of ASA and SA in a synthesized sample of aspirin.
• Incomplete reaction or inadequate washing of the product are likely
to have left the ASA contaminated with some SA.
• The same titration process can be used to determine ASA content in
commercial aspirin tablets.
• We will make use of the effective molar mass of the synthesized
samples to assay their content, but we will also take note of the
overall titration curve (see below) for confirmation of our conclusions.
This can be done for both the synthesized sample and the tablets.
• SA and ASA have significantly different molar masses. If we titrate
the same weight of the two acids with base, it will take more base to
reach the endpoint with salicylic acid, since there will be more
mmoles of acid in the sample due to its lower molar mass. A mixture
will require an intermediate amount of base.
• It can also be seen from the data above that SA is a stronger acid. The
K a of a weak acid is the equilibrium constant for the reaction in which
the acid dissociates in water. A smaller value indicates less
dissociation and therefore a weaker acid. SA is about 40 times
stronger than ASA, and we can detect this if we look at titration
curves of the two acids.
• A titration curve is a plot of the pH of a solution of the acid as a
function of the amount of base added. The stronger acid will produce
a more acidic solution (lower pH) in the lower region of the curve
prior to complete neutralization.
• The figure below illustrates calculated titration curves for 300 mg of
pure SA and 300 mg of pure ASA with 0.1 M NaOH. Remember that
the pH at the point of half-neutralization is equal to the pKa of the
acid.
Procedures
1- Accurately (on the analytical balance) weigh out ~0.2 g samples of
SA, ASA, and each of your synthesized aspirin samples.
2. Dissolve each sample in 10 mL of 95% ethanol stirring vigorously.
When the sample is completely dissolved, add 90 mL of distilled water,
and stir the solution again.
3- Add two or three drops of phenolphthalein indicator to each
solution and titrate with the standardized sodium hydroxide solution
provided. (The concentration is about 0.05 M. Record the precise value
in your notebook and on the data sheet.)
Determine the endpoint carefully by looking for formation of a
persistent light pink color.
• 5. Calculate the effective molar mass (EMM) of each sample, using
the data sheet as a guide.
• The EMM is the mass of sample in mg which produces one mmole of
H+ ions upon titration.
• For a pure compound with one acid group per molecule, this should
be the actual molar mass of the compound. For a mixture, this will be
a weighted average of the molar masses of the acid components.
• 6. If the sample consists only of ASA and SA, then the percent
composition can be derived from the EMM according to the relationships:
• %SA = 100 ( 180.15 - EMM ) / ( 180.15 - 138.12 ) = 2.379 ( 180.15 - EMM )
%ASA= 100 ( EMM - 138.12 ) / ( 180.15 - 138.12 ) = 2.379 ( EMM - 138.12 )
• Calculate the % composition of your sample.
• Note that the relationship between percent composition and EMM applies
to mixtures containing only SA and ASA! If the measured EMM is greater
than 180.15 or less than 138.12, the above formulas do not apply. Simply
report that the EMM was out of the possible range and assume the
sample consists of 100% SA or ASA, whichever is appropriate.
• If your EMM for pure SA or pure ASA differs from the expected value
by more than 10%, you should repeat that titration before proceeding
to the next part.